JP2017524775A - Red light emitting phosphor, related method and apparatus - Google Patents

Abstract

A method for synthesizing Mn4 + doped phosphors is presented. The method involves contacting a source of Mn4 + ions with a suspension containing an aqueous hydrofluoric acid solution and a complex fluoride compound of formula (II) in solid form, and then suspending the source of A + ions. Contacting the suspension to form a Mn4 + doped phosphor, Ax [MFy] (II). Where A is Li, Na, K, Rb, Cs or combinations thereof, and M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Hf, Y, La, Nb, Ta, Bi, Gd or combinations thereof, x is the absolute value of the charge of [MFy] ion, and y is 5, 6 or 7. [Selection] Figure 1

Description

  The present invention relates to red-emitting phosphors, related methods and apparatus.

Red light emitting phosphors based on complex fluoride materials activated with Mn ⁴⁺ , such as those described in US Pat. No. 7,358,542, US Pat. No. 7,497,973, and US Pat. No. 7,648,649, are yellow / green light emitting phosphors. For example, using YAG: Ce or other garnet compositions in combination with warm white light (CCT <5000K on black body locus, color rendering) from blue LEDs comparable to those produced by current fluorescent, incandescent and halogen lamps Evaluation number (CRI)> 80) can be achieved. These materials strongly absorb blue light and emit efficiently between about 610-635 nm with little dark red / NIR emission. Therefore, the luminous efficiency is maximized as compared to a red phosphor that emits a significant amount of dark red light with poor visibility. The quantum efficiency can exceed 85% under blue (440-460 nm) excitation.

  Methods for synthesizing phosphors are known as described in, for example, US Patent Application Publication No. 201220256125, International Publication No. 2007/100824, US Patent Application Publication No. 201200142189, and European Patent No. 2,508,586. However, alternative methods are desirable that can provide advantages over existing methods, such as improved phosphor properties or reduced manufacturing costs.

International Publication No. 2013/121355

Briefly, in one aspect, the invention relates to a method for synthesizing a Mn ⁴⁺ doped phosphor. In this method, a source of Mn ⁴⁺ ions is brought into contact with a suspension containing an aqueous hydrofluoric acid solution and a complex fluoride compound of the following formula (II), and then the source of A ⁺ ions is suspended in the suspension. To form a Mn ⁴⁺ doped phosphor.

A _x [MF _y ] (II)
Where
A is Li, Na, K, Rb, Cs or combinations thereof;
M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Hf, Y, La, Nb, Ta, Bi, Gd, or a combination thereof, and x is the charge of the [MF _y ] ion. Is the absolute value of
y is 5, 6 or 7.

In another aspect, the present invention relates to a Mn ⁴⁺ doped phosphor that can be produced by the method, and to an illumination device and a black light device comprising the Mn ⁴⁺ doped phosphor.

  These and other features, aspects and advantages of the present invention will become better understood when the following detailed description is read with reference to the accompanying drawings in which like characters represent like parts throughout the drawings, and wherein:

It is a figure which shows schematic sectional drawing of the illuminating device by one Embodiment of this invention. It is a figure which shows schematic sectional drawing of the illuminating device by another embodiment of this invention. It is a figure which shows schematic sectional drawing of the illuminating device by another embodiment of this invention. It is a figure which shows the fracture | rupture side perspective view of the illuminating device by 1 aspect of this invention. It is a figure which shows the schematic perspective view of a surface mount device (SMD) backlight LED.

  The approximation terms used throughout the specification and claims in this specification apply to modify any quantitative expression that may vary within acceptable limits without changing its associated basic function. May be. Thus, a value modified by one or more terms such as “about” is not limited to the exact value specified. In some examples, the word representing approximation may correspond to the accuracy of the instrument for measuring the value. In the following specification and claims, the singular forms “a”, “an”, and “the” unless the context clearly indicates otherwise. Reference to the plural form.

As used herein, the term “complex fluoride” or “complex fluoride material” contains one or more coordination centers surrounded by fluoride ions that act as ligands, optionally with counter ions. A charge-compensated coordination compound is meant. In one example, K ₂ SiF ₆ , the coordination center is Si and the counter ion is K. Although complex fluorides are sometimes described as simple binary fluoride combinations, such representations do not indicate the coordination number of the ligand around the coordination center. Square brackets (sometimes omitted for brevity) indicate that the complex ions they surround are new species and are different from simple fluoride ions. In certain embodiments, the coordination center of the complex fluoride, ie, M in formula (II), is Si, Ge, Sn, Ti, Zr, or combinations thereof. More specifically, the coordination center is Si, Ge, Ti, or a combination thereof.

Examples of complex fluorinated compounds of formula (II) include K ₂ [SiF ₆ ], K ₂ [TiF ₆ ], K ₂ [SnF ₆ ], Cs ₂ [TiF ₆ ], Rb ₂ [TiF ₆ ], Cs. ₂ [SiF ₆ ], Rb ₂ [SiF ₆ ], Na ₂ [TiF ₆ ], Na ₂ [ZrF ₆ ], K ₃ [ZrF ₇ ], K ₃ [BiF ₆ ], K ₃ [YF ₆ ], K ₃ [LaF ₆ ], K ₃ [GdF ₆ ], K ₃ [NbF ₇ ], K ₃ [TaF ₇ ] may be mentioned. In certain embodiments, the phosphor of formula (II) is K ₂ SiF ₆ .

In an Mn ⁴⁺ doped phosphor, for example, a Mn ⁴⁺ doped complex fluoride material such as K ₂ SiF ₆ : Mn ⁴⁺ , the activator ion (Mn ⁴⁺ ) also acts as a coordination center, For example, Si is replaced. The host lattice (including counterion) may further modify the excitation and emission properties of the activator ion. The coordination center of the complex fluoride composition is manganese (Mn). The counter ion, ie A in formula I and formula (II), is Na, K, Rb, Cs or a combination thereof and y is 6.

Examples of Mn ⁴⁺ doped phosphors of formula I include K ₂ [SiF ₆ ]: Mn ⁴⁺ , K ₂ [TiF ₆ ]: Mn ⁴⁺ , K ₂ [SnF ₆ ]: Mn ⁴⁺ , Cs ₂ [ TiF ₆ ]: Mn ⁴⁺ , Rb ₂ [TiF ₆ ]: Mn ⁴⁺ , Cs ₂ [SiF ₆ ]: Mn ⁴⁺ , Rb ₂ [SiF ₆ ]: Mn ⁴⁺ , Na ₂ [TiF ₆ ]: Mn ^{4 +} , Na ₂ [ZrF ₆ ]: Mn ⁴⁺ , K ₃ [ZrF ₇ ]: Mn ⁴⁺ , K ₃ [BiF ₆ ]: Mn ⁴⁺ , K ₃ [YF ₆ ]: Mn ⁴⁺ , K ₃ [LaF ₆ ]: Mn ⁴⁺ , K ₃ [GdF ₆ ]: Mn ⁴⁺ , K ₃ [NbF ₇ ]: Mn ⁴⁺ , K ₃ [TaF ₇ ]: Mn ⁴⁺ . In certain embodiments, the phosphor of formula I is K ₂ SiF ₆ : Mn ⁴⁺ .

For the synthesis of Mn ⁴⁺ doped phosphors according to embodiments of the present invention, a source of Mn ⁴⁺ ions is brought into contact with an aqueous hydrofluoric acid solution and a suspension having a complex fluoride compound of formula (II). In some embodiments, the suspension is obtained by adding the compound in solid form (ie, powder form) to the aqueous hydrofluoric acid solution at a temperature greater than about 60 ° C., and then the suspension is less than about 30 ° C. May be prepared by cooling to a temperature of In other embodiments, the suspension may be formed by precipitating the compound of formula (II) from solution. The method for precipitation is not particularly limited and is not limited, but includes polythermal precipitation, evaporation from a solvent concentrate, addition of a poor solvent, and precipitation by common ion effects. Many known methods may be used. In the polythermal method, the temperature of the concentrate is adjusted to cause precipitation; process parameters such as cooling rate may be adjusted to change the final particle size. For precipitation by the common ion effect, the compound of formula II is prepared under conditions suitable for precipitation of at least two of the source of A ⁺ ions, the source of ions of formula MF _y ^-2 , and the compound of formula II. by coupling, in particular, both the a ⁺ ion source or formula MF source of _y-2 ion or a source of a ⁺ ions and a source of the formula MF _y-2 ions, the compound of formula II May precipitate when combined with the concentrate.

  The complex fluorinated compound is present in the suspension in solid form, in particular in particulate form. In some embodiments, it is desirable to use particles having a small particle size, eg, a D50 particle size of less than about 50 μm. In certain embodiments, the D50 particle size of the particles is from about 5 μm to about 40 μm, more specifically from about 10 μm to about 30 μm. In some embodiments, the particle population of the compound is pulverized to achieve particle size reduction. The particle size distribution may be relatively narrow.

In some embodiments, the source of Mn ⁴⁺ ions is provided in the form of a solution. The solution may be prepared by dissolving (mixing) a manganese-containing compound in an aqueous hydrofluoric acid solution (HF). Suitable manganese-containing compounds are those that can either provide Mn ⁴⁺ ions directly or can be converted to another compound that provides Mn ⁴⁺ ions. In one embodiment, the manganese-containing compound does not contain metal atoms other than manganese. Examples of suitable sources of Mn ⁴⁺ ions include compounds of formula (III): A _x [MnF _y ], manganese acetate, manganese carbonate, manganese nitrate, MnF ₂ , MnF ₃ , MnCl ₃ , MnCl ₂ hydration Products, MnO ₂ , K ₂ MnF ₅ .H ₂ O, KMnO ₄ and combinations thereof. In certain embodiments, the source of Mn ⁴⁺ ions is K ₂ MnF ₆ .

A source of A ⁺ ions may be combined with a suspension in a solution of hydrofluoric acid. The source of A ⁺ ions may be a salt, and the anion corresponding to A ⁺ is fluoride, chloride, acetate, chloride, oxalate, dihydrogen phosphate or combinations thereof, in particular fluoride. It is. Suitable examples of _{materials, KF, KHF 2, LiF,} LiHF 2, NaF, NaHF 2, RbF, RbHF 2, CsF, CsHF 2, and combinations thereof. In certain embodiments, the anion is fluoride and A includes K.

The concentration of hydrofluoric acid in the aqueous solution used in the method of the present invention is generally from about 20% w / w to about 70% w / w, especially from about 40% w / w to about 55% w / w. It is. Other acids such as hexafluorosilicic acid (H ₂ SiF ₆ ) may be included in the solvent as necessary.

The above method can result in a particle population with Mn ⁴⁺ doped phosphor. In one embodiment, the Mn ⁴⁺ doped phosphor has the formula (I).

A _x [MF _y ]: Mn ⁴⁺ (I).

  In one embodiment, the particles have a core-shell structure. As used herein, a core-shell structure means that the particles have an inner core that has a chemically different composition from the outer surface or shell. In one embodiment, the particles are comprised of a core consisting of a compound of formula (II) and a first shell consisting of a compound of formula (IV) disposed in the core.

_{A x [(M 1-z} , Mn z) F y] (IV)
In the formula, 0 <z ≦ 0.2.

In some embodiments, the surface of the core particle may be substantially covered with the first shell. As used herein, “substantially” means that at least about 80%, or particularly at least about 70%, of the surface of the particle is covered with the first shell. In some embodiments, the inner core is substantially free of Mn ⁴⁺ ions. In some embodiments, Mn ⁴⁺ ions may diffuse from the first shell to the core. In some embodiments, 0 <z ≦ 0.1, more specifically 0 <z ≦ 0.06.

The addition of a source of Mn ⁴⁺ ions, a source of A ⁺ ions or both to the suspension containing the complex fluorinated compound avoids nucleation of the new particles of the compound, and the coated particles (core- It is carried out at a temperature, duration and addition rate that form a population of shell structured particles). In some embodiments, the temperature at which the source of Mn ⁴⁺ ions, the source of A ⁺ ions, or both are added to the suspension is from about 20 ° C to about 70 ° C. However, the rate of addition, number of additions, order of addition, temperature and reactant concentration may be adjusted to optimize the performance of the resulting Mn ⁴⁺ doped phosphor for a particular application.

In some embodiments, a source of tetravalent elements is further added to the suspension during or after the addition of the source of Mn ⁴⁺ ions and the source of A ⁺ ions. In one embodiment, the source of tetravalent element M is soluble in hydrofluoric acid. Examples of suitable sources of tetravalent element Si include H ₂ SiF ₆ , A ₂ SiF ₆ , SiO ₂ , SiCl ₄ , Si (OAc) ₄ and silicon tetraalkoxides such as tetraethylorthosilicate (Si (OEt)). ₄ ). Specific examples are K ₂ SiF ₆ and H ₂ SiF ₆ . Examples of suitable sources of tetravalent element Ge include GeCl ₄ , Ge (OEt) ₄ , Ge (OPr) ₄ , Ge (OMe) ₄ , GeO ₂ and combinations thereof.

The source of the tetravalent element M may be provided in the solvent used for the suspension, for example in an aqueous hydrofluoric acid solution. Tetravalent element M source of may be combined with a source of A ⁺ ions, it may be followed by addition of a source of A ⁺ ions. That is, the source of A ⁺ ions may be further added during or after the source of the tetravalent element M is added to the suspension. In a particular embodiment, a solution of K ₂ SiF ₆ as a source of M and an aqueous hydrofluoric acid solution are added to the suspension. In some embodiments, a solution comprising an aqueous hydrofluorosilicic acid (H ₂ SiF ₆ ) solution is added.

  By adding the source of the tetravalent element M, the second shell is disposed on the first shell of the phosphor particle population. In some embodiments, the phosphor particles are comprised of a core, a first shell that covers the core, and a second shell that covers the first shell. In certain embodiments, the second shell may be composed of a composition of formula (V).

A _x [(M _1-w , Mn _w ) F _y ] (V)
In the formula, 0 ≦ w ≦ z.

In some embodiments, the surface of the first shell of particles may be substantially covered with the second shell. As used herein, “substantially” means that at least about 80%, or particularly at least about 70%, of the surface of the first shell of the particles is covered by the second shell. In some embodiments, Mn ⁴⁺ ions may diffuse from the first shell to the core and the second shell. In some embodiments, 0 <w ≦ 0.1, more specifically 0 <w ≦ 0.05. If necessary, the core-shell phosphor may be processed as described in US Pat. No. 8,252,613. Alternatively, the core - shell phosphor may be treated with a solution consisting of H ₂ MF _y, a solution of H ₂ MF _y to it, the mixture of HF and H ₂ MF _y, and HF, H ₂ MF _y and II A mixture of these compounds. In some examples, the treatment can improve the properties of the core-shell phosphor, such as color stability.

After completion of the synthesis process step, the resulting phosphor may be separated from the liquid phase. The precipitate can be vacuum filtered and rinsed with a solution, such as acetic acid, hydrofluoric acid aqueous solution and / or acetone, or mixtures thereof, and then dried to receive the Mn ⁴⁺ doped phosphor. In one embodiment, the resulting fluorescence has a population of particles having a core of formula (II) and a first shell of formula (IV) covering the core. In one embodiment, the resulting fluorescence has a core of formula (II) and a first shell of formula (IV) covering the core and a second shell of formula (V) covering the first shell. Has a particle population.

In some embodiments, A is K and M is Si. More specifically, the complex fluoride compound is K ₂ [MF ₆ ], the source of Mn ⁴⁺ ions is K ₂ [MnF ₆ ], and the source of the tetravalent element M is hydrofluoro Silicic acid. In some embodiments, the compound of formula (IV) is K ₂ [(Si _1-z , Mn _z ) F ₆ ] and the compound of formula (V) is K ₂ [(Si _1-w , Mn _w ) F ₆ . The resulting phosphor doped with Mn ⁴⁺ is K ₂ SiF ₆ : Mn ⁴⁺ .

In another aspect of the present invention, the method comprises contacting a source of Mn ⁴⁺ ions with a suspension having an aqueous hydrofluoric acid solution and a complex fluoride compound in solid form, and suspending the source of A ⁺ ions. Contacting the suspension to form a Mn ⁴⁺ doped phosphor. The complex fluorinated compound is selected from the following (A) to (H).
(A) A ₂ [MF ₅ ] (wherein A is selected from Li, Na, K, Rb, Cs and combinations thereof; M is selected from Al, Ga, In and combinations thereof);
(B) A ₃ [MF ₆ ] (wherein A is selected from Li, Na, K, Rb, Cs and combinations thereof; M is selected from Al, Ga, In and combinations thereof);
(C) Zn ₂ [MF ₇ ] (wherein M is selected from Al, Ga, In and combinations thereof),
(D) A [In ₂ F ₇ ] (wherein A is selected from Li, Na, K, Rb, Cs and combinations thereof),
(E) A ₂ [MF ₆ ] (wherein A is selected from Li, Na, K, Rb, Cs and combinations thereof; M is selected from Si, Ge, Sn, Ti, Zr and combinations thereof) ,
(F) E [MF ₆ ] (wherein E is selected from Mg, Ca, Sr, Ba, Zn and combinations thereof; M is selected from Si, Ge, Sn, Ti, Zr and combinations thereof);
(G) Ba _0.65 Zr _0.35 F _2.70 and (H) A ₃ [ZrF ₇ ] (wherein A is selected from Li, Na, K, Rb, Cs and combinations thereof).

  The process steps and some compounds are as described above.

After completion of the described synthesis process steps, the Mn ⁴⁺ doped phosphor may undergo a processing process as described in US Pat. No. 8,252,613. In one embodiment, the synthesized Mn ⁴⁺ doped phosphor is contacted with a fluorine-containing oxidant in gaseous form at an elevated temperature. The temperature at which the phosphor contacts the fluorine-containing oxidant is any temperature from about 200 ° C. to about 900 ° C., particularly from about 350 ° C. to about 600 ° C., and in some embodiments from about 400 ° C. to about 575 ° C. . In various embodiments of the invention, the temperature is at least 100 ° C, in particular at least 225 ° C, more specifically at least 350 ° C. The phosphor is contacted with the oxidant for a time sufficient to improve its performance and the stability of the resulting phosphor. Since time and temperature are interrelated, they may be adjusted together. For example, the time may be increased but the temperature may be decreased, or the temperature may be increased but the time may be decreased. In certain embodiments, the time is at least 1 hour, particularly at least 4 hours, more specifically at least 6 hours, most particularly at least 8 hours.

  By reducing the temperature at a controlled rate ≦ 5 ° C./min, a phosphor product having superior properties compared to reducing at a rate of 10 ° C./min can be obtained. In various embodiments, the rate may be controlled to a rate of ≦ 5 ° C./min, in particular ≦ 3 ° C./min, more specifically ≦ 1 ° C./min.

  The time for the temperature to drop at a controlled rate is related to the contact temperature and the cooling rate. For example, if the contact temperature is 540 ° C. and the cooling rate is 10 ° C./min, the time to control the cooling rate may be less than 1 hour, then the temperature to purge or ambient temperature without external control May be reduced. If the contact temperature is 540 ° C. and the cooling rate is ≦ 5 ° C./min, the cooling time can be less than 2 hours. If the contact temperature is 540 ° C. and the cooling rate is ≦ 3 ° C./min, the cooling time can be less than 3 hours. When the contact temperature is 540 ° C. and the cooling rate is ≦ 1 ° C./min, the cooling time can be less than 4 hours. For example, the temperature may be lowered to about 200 ° C. by controlled cooling and then control may be discontinued. After a controlled period of cooling, the temperature may decrease at a rate that is higher or lower than the initial controlled rate.

Fluorine-containing oxidizing _{agent, F 2, HF, SF 6} , BrF 5, NH 4 HF 2, NH 4 F, KF, AlF 3, SbF 5, ClF 3, BrF 3, KrF, XeF 2, XeF 4, NF 3 SiF ₄ , PbF ₂ , ZnF ₂ , SnF ₂ , CdF ₂ or a combination thereof. In certain embodiments, the fluorine-containing oxidizing agent is F _2. The amount of oxidant in the atmosphere can vary to obtain the desired properties of the phosphor, particularly with time and temperature variations. When the fluorine-containing oxidizing agent is F _2, may contain at least 0.5% F ₂ in the atmosphere, in some embodiments it may be lower than the concentration it is effective. In particular, the atmosphere may contain at least 5% F ₂ , more specifically at least 20% F ₂ . The atmosphere may further include nitrogen, helium, neon, argon, krypton, xenon in any combination with a fluorine-containing oxidant. In certain embodiments, the atmosphere is composed of about 20% F ₂ and about 80% nitrogen.

  The method of contacting the phosphor with the fluorine-containing oxidant is not critical and may be accomplished in any manner sufficient to achieve the desired properties. In some embodiments, the chamber containing the phosphor may be sealed so that after the dose is metered, an overpressure is generated when the chamber is heated; in other examples, the fluorine and nitrogen mixture is Flowed through an annealing process that ensures a more uniform pressure. In some embodiments, additional doses of fluorine-containing oxidant may be introduced after a certain time.

In one embodiment, the Mn ⁴⁺ doped phosphor is further treated with a saturated solution of a composition of formula (II) in an aqueous hydrofluoric acid solution after contacting the phosphor with a fluorine-containing oxidant. The temperature at which the phosphor contacts the solution is about 20 ° C to about 50 ° C. The time required to treat the phosphor is from about 1 minute to about 5 hours, especially from about 5 minutes to about 1 hour. The concentration of hydrofluoric acid in the aqueous HF solution is about 20% w / w to about 70% w / w, especially about 40% w / w to about 70% w / w. Low concentration solutions can result in low yields of phosphor.

  Any numerical value enumerated herein is between the lower value and the upper value in increments of one unit, provided that there is a gap of at least 2 units between any lower value and any upper value. All values of are included. By way of example, amounts of ingredients or values of process variables, such as temperature, pressure, time, and the like, are stated to be, for example, 1-90, preferably 20-80, more preferably 30-70. Values such as 15-85, 22-68, 43-51, 30-32, etc. are explicitly enumerated herein. For values less than 1, one unit is considered 0.0001, 0.001, 0.01 or 0.1 as appropriate. These are only examples of what is specifically intended, and all possible combinations of numbers between the minimum and maximum values listed are also expressly stated in this application as well. It is regarded.

The amount of manganese in the resulting Mn ⁴⁺ doped phosphor is about 0.3 wt% (wt%) to about 2.5 wt%, based on the total weight of the precursor or phosphor (about 1. 2 mol% (mol%) to about 10 mol%). In some embodiments, the amount of manganese is about 0.3 wt% to about 1.5 wt% (about 1.2 mol% to about 6 mol%), particularly about 0.50 wt% to about 0.85 wt% (about 2 mol%). % To about 3.4 mol%), more specifically about 0.65 wt% to about 0.75 wt% (about 2.6 mol% to about 3 mol%). In other embodiments, the amount of manganese is about 0.75 wt% to 2.5 wt% (about 3 mol% to about 10 mol%), especially about 0.9 wt% to 1.5 wt% (about 3.5 mol% to about 10 mol%). 6 mol%), more specifically about 0.9 wt% to about 1.4 wt% (about 3.0 mol% to about 5.5 mol%), and more specifically about 0.9 wt% to about 1.3 wt% % (About 3.5 mol% to about 5.1 mol%).

  The resulting phosphor may have a particle size distribution with a D50 value of less than about 30 μm. In certain embodiments, the D50 particle size is from about 10 μm to about 20 μm. In some embodiments, the phosphor particle population has a particle size span ≦ 1. In certain embodiments, the particle size span ≦ 0.9.

Particle size span = (D90−D10) / D50
For example, as shown in Table 1 below, the particle size span is ≦ 1 for Examples 3 and 4 and ≦ 0.9 for Example 5.

  A lighting device or light emitting assembly or lamp 10 according to one embodiment of the present invention is shown in FIG. The lighting device 10 includes a semiconductor radiation source, shown as a light emitting diode (LED) chip 12, and leads 14 that are electrically connected to the LED chip. The lead 14 may be a thin wire supported by one or more thicker lead frames 16, or the lead may be a self-supporting electrode and the lead frame may be omitted. Lead 14 provides current to LED chip 12, thus causing the chip to emit radiation.

The lamp may include a semiconductor blue or ultraviolet light source capable of producing white light when its emitted radiation is directed at the phosphor. In one embodiment, the semiconductor light source is a blue light emitting LED doped with various impurities. Thus, the LED may comprise a semiconductor diode with an emission wavelength of about 250-550 nm, based on any suitable III-V, II-VI or IV-IV semiconductor layer. In particular, the LED may have one or more semiconductor layers comprising GaN, ZnSe or SiC. For example, an LED has the formula In _i Ga _j Al _k N, where the emission wavelength is greater than about 250 nm and less than about 550 nm, where 0 ≦ i; 0 ≦ j; 0 ≦ k and I + j + k = 1. Nitride compound semiconductors represented by: In certain embodiments, the chip is a near ultraviolet or blue light emitting LED with a peak emission wavelength of about 400 to about 500 nm. Such LED semiconductors are known in the art. The radiation source is described herein as an LED for convenience. However, in this specification, the term is meant to encompass all semiconductor radiation sources including, for example, semiconductor laser diodes. Further, the general discussion of the example structures of the present invention discussed herein contrasts with light sources based on inorganic LEDs, but unless otherwise noted, the LED chip may be replaced with another radiation source. It will be appreciated that references to semiconductors, semiconductor LEDs, or LED chips are merely representative of any suitable radiation source, including but not limited to organic light emitting diodes.

In the lighting device 10, the phosphor composition 22 is radiatively coupled to the LED chip 12. The phosphor composition includes the manganese (Mn ⁴⁺ ) -doped phosphor described in the above embodiment. Radiation coupled means that the radiation from one is related to each other so that it is transmitted to the other. The phosphor composition 22 is deposited on the LED 12 by any suitable method. For example, an aqueous suspension of one or more phosphors can be formed and applied to the LED surface as a phosphor layer. In one such method, a silicone slurry in which phosphor particles are randomly suspended is placed around the LED. This method is merely an example of a possible location of the phosphor composition 22 and the LED 12. Therefore, the phosphor composition 22 may be coated over the light emitting surface of the LED chip 12 or may be in direct contact with the surface by coating the phosphor suspension over the LED chip 12 and drying it. May be. In the case of silicone-based suspensions, the suspension is cured at an appropriate temperature. Both the shell 18 and the encapsulant 20 must be transparent so that white light 24 is transmitted through those elements. Without limitation, in some embodiments, the D50 particle size of the phosphor composition is about 1 to about 50 μm, particularly about 10 to about 35 μm.

  In other embodiments, the phosphor composition 22 is scattered within the encapsulant 20 instead of being formed directly on the LED chip 12. The phosphor (in the form of a powder) may be interspersed within one region of the encapsulant 20 or over the entire volume of encapsulant. The blue light emitted from the LED chip 12 is mixed with the light emitted from the phosphor composition 22, and the mixed light appears as white light. When the phosphor is dispersed in the material of the encapsulant 20, the phosphor powder is added to the polymer or silicone precursor, and the mixture is cured before or after the LED chip 12 is charged with the mixture to solidify the polymer or silicone material. It's okay. Examples of polymer precursors include thermoplastic or thermosetting polymers or resins, such as epoxy resins. Other known phosphor scattering methods, such as transfer loading, may be used.

In some embodiments, the encapsulating material 20 has a refractive index R and includes, in addition to the phosphor composition 22, a diluent material having an absorbance of less than about 5% and a refractive index of R ± 0.1. . The refractive index of the diluent material is ≦ 1.7, in particular ≦ 1.6, more specifically ≦ 1.5. In certain embodiments, the diluent material is of formula (II): A _x [MF _y ] and the refractive index is about 1.4. By adding an optically inert material to the phosphor / silicone mixture, a more gradual distribution of the light flux through the phosphor / encapsulant mixture can be generated, resulting in less damage to the phosphor. . Suitable materials for the diluent include fluoride compounds such as LiF, MgF ₂ , CaF ₂ , SrF ₂ , AlF ₃ , K ₂ NaAlF ₆ , KMgF ₃ , CaLiAlF ₆ , K ₂ LiAlF ₆ , and K ₂ SiF ₆ ( Examples include polymers having a refractive index of about 1.38 (AlF ₃ and K ₂ NaAlF ₆ ) to about 1.43 (CaF ₂ ) and about 1.254 to about 1.7. Non-limiting examples of polymers suitable for use as diluents include polycarbonate, polyester, nylon, polyetherimide, polyetherketone, and styrene, acrylate, methacrylate, vinyl, vinyl acetate, ethylene, propylene oxide, and ethylene oxide. Examples include polymers derived from monomers, and copolymers thereof, including halogenated and non-halogenated derivatives. These polymer powders can be incorporated directly into the silicone encapsulant prior to silicone curing.

  In yet another embodiment, the phosphor composition 22 is coated on the surface of the shell 18 instead of being formed over the LED chip 12. The phosphor composition is preferably coated on the inner surface of the shell 18, but the phosphor may be coated on the outer surface of the shell if desired. The phosphor composition 22 may be coated on the entire surface of the shell, or may be coated only on the upper portion of the surface of the shell. The UV / blue light emitted from the LED chip 12 is mixed with the light emitted from the phosphor composition 22, and the mixed light appears as white light. Of course, the phosphor may be located at any two or all three locations, or at any other suitable location, eg, separate from the shell or at a location incorporated in the LED.

  FIG. 2 illustrates a second structure of the system according to the invention. Corresponding numbers in FIGS. 1-4 (eg, 12 in FIG. 1 and 112 in FIG. 2) relate to the corresponding structure of each of the figures unless otherwise specified. The structure of the embodiment of FIG. 2 is similar to the structure of FIG. 1 except that the phosphor composition 122 is scattered inside the encapsulant 120 instead of being formed directly on the LED chip 112. Yes. The phosphor (in powder form) may be interspersed within one region of the encapsulant material or over the entire volume of the encapsulant material. The radiation emitted by the LED chip 112 (indicated by the arrow 126) is mixed with the light emitted by the phosphor 122, and the mixed light appears as white light 124. When the phosphor is scattered inside the encapsulating material 120, the phosphor powder may be added to the polymer precursor and filled around the LED chip 112. The polymer or silicone precursor may then be cured by curing the polymer or silicone. Other known phosphor scattering methods such as transfer molding may be used.

  FIG. 3 illustrates a third possible structure of the system according to the invention. The structure of the embodiment shown in FIG. 3 is similar to the structure of FIG. 1 except that the phosphor composition 222 is coated on the surface of the envelope 218 instead of being formed over the LED chip 212. Yes. The phosphor composition 222 is preferably coated on the inner surface of the envelope 218, but the phosphor may be coated on the outer surface of the envelope as needed. The phosphor composition 222 may be coated on the entire surface of the envelope, or may be coated only on the upper surface of the envelope. The radiation 226 emitted from the LED chip 212 is mixed with the light emitted from the phosphor composition 222, and the mixed light appears as white light 224. Of course, the structures of FIGS. 1-3 can be combined, and the phosphor can be incorporated in any two or all three locations, or any other suitable location, such as separately from the envelope or in the LED It may be located at a certain position.

  In any of the above structures, the lamp may also include a plurality of scattering particles (not shown) embedded in the encapsulating material. The scattering particles may include, for example, alumina or titania. The scattering particles efficiently scatter directional light emitted from the LED chip, and preferably have very little absorption.

  As shown in the fourth structure of FIG. 4, the LED chip 412 may be mounted on the reflective cup 430. Cup 430 may be formed or coated with a dielectric, such as alumina, titania, or other dielectric powder known in the art, or may be coated with a reflective metal, such as aluminum or silver. . The remaining portion of the structure of the embodiment of FIG. 4 is the same as any portion of the previous figure, and may include two leads 416, a conductive wire 432, and an encapsulating material 420. The reflective cup 430 is supported by the first lead 416, and the conductive wire 432 is used to electrically connect the second lead 416 and the LED chip 412.

Another structure (especially for backlight applications) is a surface mount device (“SMD”) type light emitting diode 550, for example as illustrated in FIG. This SMD is a “side light emission type”, and has a light emission window 552 on the protruding portion of the light guide member 554. The SMD package may include an LED chip as defined above and a phosphor material that is excited by light emitted from the LED chip. Other black light devices include, but are not limited to, TVs, computers, monitors, smartphones, tablet computers, and semiconductor light sources; and other portables having displays that include Mn ⁴⁺ doped phosphors according to the present invention. Device.

  When used in combination with LEDs emitting at 350-550 nm and one or more other suitable phosphors, the resulting lighting device produces white light. The lamp 10 may also include a plurality of scattering particles (not shown) embedded in the encapsulating material. The scattering particles may include, for example, alumina or titania. The scattering particles efficiently scatter directional light emitted from the LED chip, and preferably have very little absorption.

In addition to the Mn ⁴⁺ doped phosphor, the phosphor composition 22 may include one or more other phosphors. When used in an illuminator in combination with a blue or near-ultraviolet LED that emits radiation in the range of about 250-550 nm, the resulting light emitted from this assembly is white light. Other phosphors, such as green, blue, yellow, red, orange, and other color phosphors, can be used in the blend to customize the resulting white color of the light and generate a specific spectral power distribution. Good. Other materials suitable for use in phosphor composition 22 include electroluminescent polymers such as polyfluorenes, preferably poly (9,9-dioctylfluorene) and copolymers thereof such as poly (9,9 ′. -Dioctylfluorene-co-bis-N, N '-(4-butylphenyl) diphenylamine) (F8-TFB); poly (vinyl carbazole) and polyphenylene vinylene and their derivatives. In addition, the light emitting layer may include blue, yellow, orange, green or red phosphorescent dyes or metal complexes, or combinations thereof. Materials suitable for use as the phosphorescent dye include, but are not limited to, tris (1-phenylisoquinoline) iridium (III) (red dye), tris (2-phenylpyridine) iridium (green dye) And iridium (III) bis (2- (4,6-difluorphenyl) pyridinato-N, C2) (blue dye). Fluorescent and phosphorescent metal complexes commercially available from ADS (American Dies Source, Inc.) may be used. ADS green pigments include ADS060GE, ADS061GE, ADS063GE, and ADS066GE, ADS078GE, and ADS090GE. ADS blue pigments include ADS064BE, ADS065BE, and ADS070BE. Examples of the ADS red dye include ADS067RE, ADS068RE, ADS069RE, ADS075RE, ADS076RE, ADS067RE, and ADS077RE.

Phosphors suitable for use in phosphor composition 22 include, but are not limited to:
_{((Sr 1-z (Ca} , Ba, Mg, Zn) z) 1- (x + w) (Li, Na, K, Rb) w Ce x) 3 (Al 1-y Si y) O 4 + y _{+3 (xw)} F _{1-y-3 (xw)} (0 <x ≦ 0.10, 0 ≦ y ≦ 0.5, 0 ≦ z ≦ 0.5, 0 ≦ w ≦ x);
(Ca, Ce) ₃ Sc ₂ Si ₃ O ₁₂ (CaSiG);
_{(Sr, Ca, Ba) 3} Al 1-x Si x O 4 + x F 1-x: Ce 3+ (SASOF));
(Ba, Sr, Ca) ₅ (PO ₄ ) ₃ (Cl, F, Br, OH): Eu ²⁺ , Mn ²⁺ ; (Ba, Sr, Ca) BPO ₅ : Eu ²⁺ , Mn ²⁺ ; Sr, Ca) ₁₀ (PO ₄ ) ₆ * νB ₂ O ₃ : Eu ²⁺ (0 <ν ≦ 1); Sr ₂ Si ₃ O ₈ * 2SrCl ₂ : Eu ²⁺ ; (Ca, Sr, Ba) ₃ MgSi ₂ O ₈ : Eu ²⁺ , Mn ²⁺ ; BaAl ₈ O ₁₃ : Eu ²⁺ ; 2SrO * 0.84P ₂ O ₅ * 0.16 B ₂ O ₃ : Eu ²⁺ ; (Ba, Sr, Ca) MgAl _{10 ^{O 17: Eu 2+, Mn 2+}} ; (Ba, Sr, Ca) Al 2 O 4: Eu 2+; (Y, Gd, Lu, Sc, La) BO 3: Ce 3+, Tb 3+; ZnS : Cu ⁺ , Cl ⁻ ; ZnS: Cu ⁺ , Al ³⁺ ; ZnS: Ag ⁺ , Cl ⁻ ; ZnS: Ag ⁺ , Al ³⁺ ; (Ba, Sr, Ca) ₂ Si ₁₋ ξO _4-2 ξ: Eu ²⁺ (0.2 ξ ≦ 0.2); (Ba, Sr, Ca) 2 (Mg, Zn) Si 2 O 7: Eu 2+; (Sr, Ca, Ba) (Al, Ga, In) 2 S 4: Eu 2+ (Y, Gd, Tb, La, Sm, Pr, Lu) ₃ (Al, Ga) _5- αO _{12-3 / 2} α: Ce ³⁺ (0 ≦ α ≦ 0.5); (Ca, Sr) ₈ (Mg, Zn) (SiO ₄ ) ₄ Cl ₂ : Eu ²⁺ , Mn ²⁺ ; Na ₂ Gd ₂ B ₂ O ₇ : Ce ³⁺ , Tb ³⁺ ; (Sr, Ca, Ba, Mg, Zn) ^{_{2 P 2 O 7: Eu 2+}} , Mn 2+; (Gd, Y, Lu, La) 2 O 3: Eu 3+, Bi 3+; (Gd, Y, Lu, La) 2 O 2 S: Eu ³⁺ , Bi ³⁺ ; (Gd, Y, Lu, La) VO ₄ : Eu ³⁺ , Bi ³⁺ ; (Ca, Sr) S: Eu ²⁺ , Ce ³⁺ ; SrY ₂ S ₄ : Eu ^{2+ _{; CaLa 2 S 4: Ce 3+}} ; (Ba, Sr, Ca) MgP 2 O 7: E ^{2+, Mn 2+; (Y,} Lu) 2 WO 6: Eu 3+, Mo 6+; (Ba, Sr, Ca) βSiγNμ: Eu 2+ (2β + 4γ = 3μ); (Ba, Sr, Ca) 2 _{Si 5-x Al x N 8} -x O x: Eu 2+ (0 ≦ x ≦ 2); Ca 3 (SiO 4) Cl 2: Eu 2+; (Lu, Sc, Y, Tb) 2-uv Ce _v Ca _{1 + u} Li _w Mg _2-w P _w (Si, Ge) _3-w O _{12-u / 2} (−0.5 ≦ u ≦ 1, 0 <v ≦ 0.1, and 0 ≦ w ≦ 0.2); (Y, Lu, Gd) _2- φCaφSi ₄ N ₆₊ φC ₁₋ φ: Ce ³⁺ , (0 ≦ φ ≦ 0.5); doped with Eu ²⁺ and / or Ce ³⁺ (Lu, Ca, Li, Mg, Y), α-SiAlON; (Ca, Sr, Ba) SiO ₂ N ₂ : Eu ²⁺ , Ce ³⁺ ; β-SiAlON: Eu ²⁺ , 3.5MgO * 0. ^{_{5MgF 2 * GeO 2: Mn 4+}} ; (Sr, Ca, Ba) Al ^{_{iN 3: Eu 2+; (Sr}} , Ca, Ba) 3 SiO 5: Eu 2+; Ca 1-cf Ce c Eu f Al 1 + c Si 1-c N 3 (0 ≦ c ≦ 0.2,0 _{≦ f ≦ 0.2); Ca 1} -hr Ce h Eu r Al 1-h (Mg, Zn) h SiN 3 (0 ≦ h ≦ 0.2,0 ≦ r ≦ 0.2);
Ca _1-2s-t Ce _s (Li, Na) _s Eu _t AlSiN ₃ (0 ≦ s ≦ 0.2, 0 ≦ f ≦ 0.2, s + t>0); and Ca ₁₋ σ ₋ χ ₋ φCeσ ( _{li, Na) χEuφAl 1+ σ -} χSi 1- σ + χN 3 (0 ≦ σ ≦ 0.2,0 ≦ χ ≦ 0.4,0 ≦ φ ≦ 0.2).

The ratio of each individual phosphor in the phosphor blend may vary depending on the desired light output characteristics. The relative proportions of the individual phosphors in the phosphor blends of the various embodiments are determined by the predetermined x value on the CIE chromaticity diagram and their emission when used in an LED lighting device and It may be adjusted so that visible light with a y value is generated. As mentioned, white light is preferably generated. This white light may have, by way of example, an x value in the range of about 0.20 to about 0.55 and a y value in the range of about 0.20 to about 0.55. However, as stated, the exact identity and amount of each phosphor in the phosphor composition can vary depending on the end user's requirements. For example, this material can be used in LEDs intended for liquid crystal display (LCD) backlights. In the child application, the LED color point is adjusted appropriately based on the desired white, red, green, and blue color after passing through the LCD / color filter combination. The list of potential phosphors for the blends described herein is not exhaustive, and these Mn ⁴⁺ doped phosphors are used to achieve the desired spectral power distribution. Can be blended with various phosphors with different emission.

The Mn ⁴⁺ doped phosphor of the present invention may be used for applications other than those described above. For example, this material may be used as a phosphor in a fluorescent lamp, cathode ray tube, plasma display device or liquid crystal display (LCD). This material may also be used as an electromagnetic calorimeter, gamma camera, computed tomography scanner or laser scintillator. These uses are merely examples and are not limiting.

  The following examples are for illustrative purposes only and should not be construed as any kind of limitation on the scope of the claimed invention.

Preparation of K ₂ SiF ₆
Example 1
Coarse particles were removed by ball milling K ₂ SiF ₆ (100 g) (Aldrich) for 1 hour followed by sieving through a 44 μm sieve. The resulting particles had a D50 particle size of 19 μm.

Example 2
KF (13 g) was added to 80 milliliters (ml) of 48% HF. H ₂ SiF ₆ (35%) (30 ml) was added to 30 ml of 48% HF. Both solutions were stirred separately and then the H ₂ SiF ₆ / HF solution was added to the KF / HF solution. The resulting K ₂ SiF ₆ particles had a D50 particle size of 15 μm.

Synthesis of manganese (Mn ⁴⁺ ) doped K ₂ SiF ₆ (PFS phosphor)
Example 3
The K ₂ SiF ₆ (16 g) particles prepared in Example 1 were added to a beaker containing 130 milliliters (ml) of 48% HF. The suspension was stirred for 10 minutes. KHF ₂ (8 g) was added with stirring to a beaker containing 20 ml of 48% HF. K ₂ MnF ₆ (2 g) was added to a beaker containing 30 mL of 48% HF and the solution was stirred for 5 minutes. To the stirred K ₂ SiF ₆ suspension, the K ₂ MnF ₆ solution was added dropwise at 4 ml / min. After the K ₂ MnF ₆ solution was added dropwise for 3 minutes, the KHF ₂ solution was added to the same beaker at a rate of 3 ml / min. When the addition of KHF ₂ was complete, the suspension was stirred for an additional 10 minutes. After stopping the stirring, the supernatant was decanted and the resulting phosphor material was vacuum filtered, rinsed once with acetic acid and twice with acetone, and then dried in vacuo overnight.

Example 4
The K ₂ SiF ₆ (8 g) particles prepared in Example 1 were added to a beaker containing 130 ml of 48% HF. The suspension was stirred for 10 minutes. KF (4.5 g) was added with stirring to a beaker containing 20 ml of 48% HF. Since this method is very exothermic, the KF solution was allowed to cool for several minutes. K ₂ MnF ₆ (1.5 g) was added to a beaker containing 30 ml of 48% HF and the solution was stirred for 5 minutes. To a stirred suspension of K ₂ SiF ₆ particles, the K ₂ MnF ₆ solution was added dropwise at 4 ml / min. After the K ₂ MnF ₆ solution was added dropwise for 3 minutes, the KF solution was added to the same beaker at a rate of 3 ml / min. When the addition of KF was complete, the suspension was stirred for an additional 5 minutes. After stopping the stirring, the supernatant was decanted and the resulting phosphor material was vacuum filtered, rinsed once with acetic acid and twice with acetone, and then dried in vacuo overnight.

Example 5
The K ₂ SiF ₆ (12 g) particles prepared in Example 1 were added to a beaker containing 130 ml of 48% HF. The suspension was stirred for 10 minutes. KF (8 g) was added with stirring to a second beaker containing 20 ml of 48% HF. Since this method is very exothermic, the KF solution was allowed to cool for several minutes. K ₂ MnF ₆ (2 g) was added to a third beaker containing 30 ml of 48% HF and the solution was stirred for 5 minutes. To a fourth beaker, 4 ml of 35% H ₂ SiF ₆ , 12 mL of 48% HF was added and stirred. To the stirred solution of K ₂ SiF ₆ particles, the K ₂ MnF ₆ solution was added dropwise at 4 ml / min. After the K ₂ MnF ₆ solution was added dropwise for 3 minutes, the KF solution was added to the same beaker at a rate of 3 ml / min. After the K ₂ MnF ₆ solution was dropped for 4 minutes, the H ₂ SiF ₆ solution was dropped at a rate of 3 ml / min. When the addition of H ₂ SiF ₆ was complete, the suspension was stirred for an additional 5 minutes. After stopping the stirring, the supernatant was decanted and the resulting phosphor material was vacuum filtered, rinsed once with acetic acid and twice with acetone, and then dried in vacuo overnight.

The emission spectra of the phosphor materials of Example 3, Example 4 and Example 5 were individually obtained, and it was observed that the emission spectra of the three samples were comparable to the emission spectrum of K ₂ SiF ₆ : Mn ⁴⁺ . Table 1 shows the spectral characteristics of the three samples.

Example 6
K ₂ SiF ₆ (8 g) particles were added to a beaker containing 160 ml of 48% HF. The mixture was stirred for 30 minutes and then vacuum filtered to remove undissolved K ₂ SiF ₆ . Solution 1 was prepared by adding 30 ml of 35% H ₂ SiF ₆ to 120 ml of 48% HF. Solution 2 was prepared by adding 5.47 g KF to 12 ml HF. Solution 3 was prepared by adding 1.5 g K ₂ MnF ₆ to 30 ml HF. Three solutions, Solution 1, Solution 2, and Solution 3, were added dropwise to the filtrate. Initially, the addition of Solution 3 was delayed for Solution 1 and Solution 2. A core with a low Mn ⁴⁺ concentration and a shell rich in Mn ⁴⁺ were obtained. In some cases, extending the duration of addition of Solution 1 and / or Solution 2 to Solution 3 resulted in additional shells with lower Mn ⁴⁺ concentrations.

  While only certain features of the invention have been illustrated and described herein, many modifications and changes will occur to those skilled in the art. Therefore, it will be understood that the appended claims are intended to cover all such modifications and changes as fall within the true spirit of this invention.

Claims (25)

A method for synthesizing a Mn ⁴⁺ doped phosphor,
Contacting a source of Mn ⁴⁺ ions with a suspension containing an aqueous hydrofluoric acid solution and a complex fluoride compound of the following formula (II) in solid form;
Contacting the suspension with a source of A ⁺ ions to form a Mn ⁴⁺ doped phosphor.
A _x [MF _y ] (II)
Where
A is Li, Na, K, Rb, Cs or combinations thereof;
M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Hf, Y, La, Nb, Ta, Bi, Gd, or a combination thereof, and x is the charge of the [MF _y ] ion. Is the absolute value of
y is 5, 6 or 7. The method of claim 1, further comprising contacting the source of tetravalent element M with the suspension after contacting the source of A ⁺ ions. The method according to claim 2, wherein the source of the tetravalent element M is R ₂ MF ₆ (wherein R is H or A). 3. The method of claim 2, further comprising contacting the suspension with a source of A ⁺ ions together with a source of tetravalent element M.   The method of claim 1, wherein A is Na, K, Rb, Cs, or a combination thereof, M is Si, Ge, Ti, or a combination thereof, and Y is 6. The method of claim 1, wherein the source of Mn ⁴⁺ ions is K ₂ MnF ₆ . Complex fluoride compound of the formula (II) is K ₂ SiF _6, The method of claim 1. The method of claim 1, wherein the Mn ⁴⁺ doped phosphor is of formula I
A _x [MF _y ]: Mn ⁴⁺
(I) Mn ⁴⁺ doped phosphor K ₂ SiF ₆ of Formula I: a Mn ^4+, The method of claim 8. The method of claim 1, wherein the A ⁺ ions are derived from KF, KHF ₂ or combinations thereof. The method of claim 1, further comprising contacting the Mn ⁴⁺ doped phosphor with a fluorine-containing oxidant at an elevated temperature. ^{12. The} method of claim 11, further comprising contacting the Mn ⁴⁺ doped phosphor with a saturated solution of a compound of formula (II) in an aqueous hydrofluoric acid solution after contacting the phosphor and the fluorine-containing oxidant. the method of. A Mn ⁴⁺ doped phosphor produced by the method according to claim 1. A lighting device comprising a semiconductor light source and a Mn ⁴⁺ doped phosphor produced by the method according to claim 1. A black light device comprising a semiconductor light source and a Mn ⁴⁺ doped phosphor produced by the method according to claim 1. A method for synthesizing a Mn ⁴⁺ doped phosphor,
Contacting a source of Mn ⁴⁺ ions with a suspension containing an aqueous hydrofluoric acid solution and a complex fluoride compound in solid form;
Forming a Mn ⁴⁺ doped phosphor by bringing a source of A ⁺ ions into contact with the suspension, and the complex fluorinated compound comprises the following (A) to (H):
(A) A ₂ [MF ₅ ] (wherein M is selected from Al, Ga, In and combinations thereof),
(B) A ₃ [MF ₆ ] (wherein M is selected from Al, Ga, In and combinations thereof),
(C) Zn ₂ [MF ₇ ] (wherein M is selected from Al, Ga, In and combinations thereof),
(D) A [In ₂ F ₇ ],
(E) A ₂ [MF ₆ ] (wherein M is selected from Si, Ge, Sn, Ti, Zr and combinations thereof),
(F) E [MF ₆ ] (wherein E is selected from Mg, Ca, Sr, Ba, Zn and combinations thereof; M is selected from Si, Ge, Sn, Ti, Zr and combinations thereof) ),
(G) Ba _0.65 Zr _0.35 F _2.70 and (H) A ₃ [ZrF ₇ ]
The method wherein A is Li, Na, K, Rb, Cs or combinations thereof selected from the group consisting of A Mn ⁴⁺ doped phosphor produced by the method according to claim 16. A particle population comprising a core and a first shell, wherein the core comprises a compound of formula (II):
A _x [MF _y ] (II)
A particle population, wherein the first shell comprises a composition of formula (IV):
_{A x (M 1-z,} Mn z) F y] (IV)
Where
A is Li, Na, K, Rb, Cs, NR ₄ or a combination thereof;
M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Hf, Y, La, Nb, Ta, Bi, Gd or a combination thereof, and x is the charge of the [MFy] ion Absolute value,
y is 5, 6 or 7;
0 <z ≦ 0.2. The particle population of claim 18 further comprising a second shell, wherein the second shell comprises a composition of the following formula (V):
A _x [(M _1-w , Mn _w ) F _y ] (V)
In the formula, 0 ≦ w ≦ z.
The particle population of claim 18 comprising:   The particle population of claim 18 having a particle size distribution with a particle size span of 1 or less.   The particle population of claim 18 having a particle size distribution with a particle size span of 0.9 or less. Core is K ₂ SiF _6, the first shell is _{K 2 (Si 1-z,} Mn z) is F _6, grain population of claim 18. The particle population of claim 19, wherein the second shell is K ₂ (Si _1-w , Mn _w ) F ₆ .   An illumination device comprising: a semiconductor light source; and the particle population according to claim 18 radiatively coupled to the light source.   A black light device comprising a semiconductor light source and the particle population of claim 18 radiatively coupled to the light source.